The hybridization between oxygen 2p and transition-metal 3d states largely determines the electronic structure near the Fermi level and related functionalities of transition-metal oxides(TMOs).Considerable efforts hav...The hybridization between oxygen 2p and transition-metal 3d states largely determines the electronic structure near the Fermi level and related functionalities of transition-metal oxides(TMOs).Considerable efforts have been made to manipulate the p-d hybridization in TMOs by tailoring the spatial orbital overlap via structural engineering.Here,we demonstrate enhanced p-d hybridization in Ba^(2+)-doped LaNiO_(3)epitaxial films by simultaneously modifying both the spatial and energetic overlaps between the O-2p and Ni-3d orbitals.Combining x-ray absorption spectroscopy and firstprinciples calculations,we reveal that the enhanced hybridization stems from the synergistic effects of a reduced chargetransfer energy due to hole injection and an increased spatial orbital overlap due to straightening of Ni-O-Ni bonds.We further show that the enhanced p-d hybridization can be utilized to promote the oxygen evolution activity of LaNiO_(3).This work sheds new insights into the fine-tuning of the electronic structures of TMOs for enhanced functionalities.展开更多
Hybridization is a driving force in ecological transitions and speciation,yet direct evidence linking it to adaptive differentiation in natural systems remains limited.This study evaluates the role of hybridization in...Hybridization is a driving force in ecological transitions and speciation,yet direct evidence linking it to adaptive differentiation in natural systems remains limited.This study evaluates the role of hybridization in the speciation of Pinus densata,a keystone forest species on the southeastern Tibetan Plateau.By creating artificialinterspecificF1s and a long-term common garden experiment on the plateau,we provide in situ assessments on 44 growth and physiological traits across four seasons,along with RNA sequencing.We found significantphenotypic divergence between P.densata and its putative parental species P.tabuliformis and P.yunnanensis,with P.densata demonstrating superior growth and dynamic balance between photosynthesis and photoprotection.The F1s closely resembled P.densata in most traits.Gene expression revealed 19%–10%of 34,000 examined genes as differentially expressed in P.densata and F1s relative to mid-parent expression values.Both additive(4%)and non-additive gene actions(5%–6%in F1s,10%–12%in P.densata)were common,while transgressive expression occurred more frequently in the stabilized natural hybrids,illustrating transcriptomic reprogramming brought by hybridization and further divergence by natural selection.We provide compelling evidence for hybridization-derived phenotypic divergence at both physiological and gene expression levels that could have contributed to the adaptation of P.densata to high plateau habitat where both parental species have low fitness.The altered physiology and gene expression in hybrids serve both as a substrate for novel ecological adaptation and as a mechanism for the initiation of reproductive isolation.展开更多
Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.H...Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.Herein,we find that oxygen vacancies can significantly boost the capacity,electrochemical kinetics,and structure stability of LDHs.The corresponding structure-performance relationship and energy storage mechanism are elaborated through exhaustive in/ex-situ experimental characterizations and density functional theory(DFT)calculations.Specially,in-situ Raman and DFT calculations reveal that oxygen vacancies elevate orbital energy of O 2p and electron density of O atoms,thereby enhancing the orbital hybridization of O 2p with Ni/Co 3d.This facilitates electron transfer between O and adjacent Ni/Co atoms and improves the covalency of Ni–O and Co–O bonds,which activates Ni/Co atoms to release more capacity and stabilizes the Ov-NiCo-LDH structure.Moreover,the distribution of relaxation times(DRT)and molecular dynamics(MD)simulations disclose that the enhanced d-p orbital hybridization optimizes the electronic structure of Ov-NiCo-LDH,which distinctly reduces the diffusion energy barriers of Mg^(2+)and improves the charge transfer kinetics of Ov-NiCo-LDH.Consequently,the assembled Ov-NiCo-LDH//active carbon(AC)and Ov-NiCo-LDH//perylenediimide(PTCDI)AMIBs can both deliver high specific discharge capacity(182.7 and 59.4 mAh g^(−1)at 0.5 A g^(−1),respectively)and long-term cycling stability(85.4%and 89.0%of capacity retentions after 2500 and 2400 cycles at 1.0 A g^(−1),respectively).In addition,the practical prospects for Ov-NiCo-LDH-based AMIBs have been demonstrated in different application scenarios.This work not only provides an effective strategy for obtaining high-performance cathodes of AMIBs,but also fundamentally elucidates the inherent mechanisms.展开更多
Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains un...Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains unclear.Additionally,the modulation of reactive oxygen species in Fenton-like reactions remains challenging.Herein,a novel strategy is reported for the rational design of highly loaded Co ASACs(CoN_(1)C_(2)/C_(2)N)immobilized on three-dimensional flower-like C_(2)N using an in situ-generated carbon defect method.In particular,the asymmetrically tricoordinated CoN_(1)C_(2)/C_(2)N exhibited excellent catalytic activity for sulfachloropyridazine degradation,with a turnover frequency of 36.8 min^(–1).Experimental results and theoretical calculations revealed that the electron spin state of the Co-active sites was transferred from the low-spin configuration(t_(2g)^(6)e_(g)^(1))to the high-spin configuration(t_(2g)^(5)e_(g)^(2))owing to asymmetric coordination.The high-spin Co 3d orbital in CoN_(1)C_(2)/C_(2)N possessed more unpaired electrons and therefore,had a strong ability to gain electrons from the O 2p orbitals of HSO_(5)^(–),boosting d-p orbital hybridization.More importantly,the spin-electron filling in theσ^(*)orbital of high-spin Co 3d−O 2p accelerated the desorption of^(*)SO_(5)•^(−),which acted as a rate-limiting step in the reaction,thus facilitating more^(1)O_(2)generation.This study provides an innovative synthetic route for practical ASACs and clarifies the critical relationship between structure and spin state,paving the way for advancements in environmental remediation and energy conversion applications.展开更多
The biological species concept defines species as groups of actually or potentially interbreeding natural populations that are reproductively isolated from other such groups(Mayr,1942).Reproductive isolation,whether p...The biological species concept defines species as groups of actually or potentially interbreeding natural populations that are reproductively isolated from other such groups(Mayr,1942).Reproductive isolation,whether prezygotic or postzygotic,plays a central role in maintaining species boundaries.However,hybridization between closely related taxa can challenge these boundaries and provide insight into speciation,gene flow,and evolutionary processes(Coyne and Orr,2004).展开更多
Introduction Early cancer detection represents a critical evolution in healthcare,addressing a significant pain point in cancer treatment:the tendency for diagnoses to occur at advanced stages.Traditionally,many cance...Introduction Early cancer detection represents a critical evolution in healthcare,addressing a significant pain point in cancer treatment:the tendency for diagnoses to occur at advanced stages.Traditionally,many cancers are not identified until they have progressed to late stages,where treatment options become limited,less effective,and more costly.This late detection results in poorer prognoses,higher mortality rates,and increased healthcare costs.Without early detection tools like Fluorescence In Situ Hybridization(FISH),these challenges persist,leaving patients with fewer opportunities for successful outcomes.展开更多
Photocatalytic hydrogen(H_(2))production using solar energy is a cutting-edge green technology that holds great potential for addressing the urgent fuel and environmental crises[1–3].To achieve high-efficiency H_(2) ...Photocatalytic hydrogen(H_(2))production using solar energy is a cutting-edge green technology that holds great potential for addressing the urgent fuel and environmental crises[1–3].To achieve high-efficiency H_(2) production,cocatalyst modification is commonly employed to provide active sites for the hydrogen evolution reaction(HER)[4,5].In this context,the kinetics of hydrogen adsorption and desorption at these active sites play a crucial role in enhancing overall photocatalytic H_(2) production efficiency.However,the H adsorption/desorption kinetics often exhibit a trade-off,presenting a significant challenge in achieving an optimal equilibrium between Hads and Hdes in many cocatalyst systems.Therefore,fine-tuning the active sites to optimize the H_(2) evolution kinetics is essential for improving photocatalytic activity[6].展开更多
DNA nanomaterials hold great promise in biomedical fields due to its excellent sequence programmability,molecular recognition ability and biocompatibility.Hybridization chain reaction(HCR)is a simple and efficient iso...DNA nanomaterials hold great promise in biomedical fields due to its excellent sequence programmability,molecular recognition ability and biocompatibility.Hybridization chain reaction(HCR)is a simple and efficient isothermal enzyme-free amplification strategy of DNA,generating nicked double helices with repeated units.Through the design of HCR hairpins,multiple nanomaterials with desired functions are assembled by DNA,exhibiting great potential in biomedical applications.Herein,the recent progress of HCR-based DNA nanomaterials for biosensing,bioimaging and therapeutics are summarized.Representative works are exemplified to demonstrate how HCR-based DNA nanomaterials are designed and constructed.The challenges and prospects of the development of HCR-based DNA nanomaterials are discussed.We envision that rationally designing HCR-based DNA nanomaterials will facilitate the development of biomedical applications.展开更多
The rational design of metal single-atom catalysts(SACs)for electrochemical nitrogen reduction reaction(NRR)is challenging.Two-dimensional metal-organic frameworks(2DMOFs)is a unique class of promising SACs.Up to now,...The rational design of metal single-atom catalysts(SACs)for electrochemical nitrogen reduction reaction(NRR)is challenging.Two-dimensional metal-organic frameworks(2DMOFs)is a unique class of promising SACs.Up to now,the roles of individual metals,coordination atoms,and their synergy effect on the electroanalytic performance remain unclear.Therefore,in this work,a series of 2DMOFs with different metals and coordinating atoms are systematically investigated as electrocatalysts for ammonia synthesis using density functional theory calculations.For a specific metal,a proper metal-intermediate atoms p-d orbital hybridization interaction strength is found to be a key indicator for their NRR catalytic activities.The hybridization interaction strength can be quantitatively described with the p-/d-band center energy difference(Δd-p),which is found to be a sufficient descriptor for both the p-d hybridization strength and the NRR performance.The maximum free energy change(ΔG_(max))andΔd-p have a volcanic relationship with OsC_(4)(Se)_(4)located at the apex of the volcanic curve,showing the best NRR performance.The asymmetrical coordination environment could regulate the band structure subtly in terms of band overlap and positions.This work may shed new light on the application of orbital engineering in electrocatalytic NRR activity and especially promotes the rational design for SACs.展开更多
Geological discontinuity(GD)plays a pivotal role in determining the catastrophic mechanical failure of jointed rock masses.Accurate and efficient acquisition of GD networks is essential for characterizing and understa...Geological discontinuity(GD)plays a pivotal role in determining the catastrophic mechanical failure of jointed rock masses.Accurate and efficient acquisition of GD networks is essential for characterizing and understanding the progressive damage mechanisms of slopes based on monitoring image data.Inspired by recent advances in computer vision,deep learning(DL)models have been widely utilized for image-based fracture identification.The multi-scale characteristics,image resolution and annotation quality of images will cause a scale-space effect(SSE)that makes features indistinguishable from noise,directly affecting the accuracy.However,this effect has not received adequate attention.Herein,we try to address this gap by collecting slope images at various proportional scales and constructing multi-scale datasets using image processing techniques.Next,we quantify the intensity of feature signals using metrics such as peak signal-to-noise ratio(PSNR)and structural similarity(SSIM).Combining these metrics with the scale-space theory,we investigate the influence of the SSE on the differentiation of multi-scale features and the accuracy of recognition.It is found that augmenting the image's detail capacity does not always yield benefits for vision-based recognition models.In light of these observations,we propose a scale hybridization approach based on the diffusion mechanism of scale-space representation.The results show that scale hybridization strengthens the tolerance of multi-scale feature recognition under complex environmental noise interference and significantly enhances the recognition accuracy of GD.It also facilitates the objective understanding,description and analysis of the rock behavior and stability of slopes from the perspective of image data.展开更多
Precisely refining the electronic structure of electrocatalysts represents a powerful approach to further optimize the electrocatalytic performance.Herein,we demonstrate an ingenious d-d orbital hybridization concept ...Precisely refining the electronic structure of electrocatalysts represents a powerful approach to further optimize the electrocatalytic performance.Herein,we demonstrate an ingenious d-d orbital hybridization concept to construct Mo-doped Co_(9)S_(8) nanorod arrays aligned on carbon cloth(CC)substrate(abbreviated as Mo-Co_(9)S_(8)@CC hereafter)as a high-efficiency bifunctional electrocatalyst toward water electrolysis.It has experimentally and theoretically validated that the 4d-3d orbital coupling between Mo dopant and Co site can effectively optimize the H_(2)O activation energy and lower H^(*)adsorption energy barrier,thereby leading to enhanced hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activities.Thanks to the unique electronic and geometrical advantages,the optimized Mo-Co_(9)S_(8)@CC with appropriate Mo content exhibits outstanding bifunctional performance in alkaline solution,with the overpotentials of 75 and 234 mV for the delivery of a current density of 10 mA cm^(-2),small Tafel slopes of 53.8 and 39.9 mV dec~(-1)and long-term stabilities for at least 32 and 30 h for HER and OER,respectively.More impressively,a water splitting electrolylzer assembled by the self-supported Mo-Co_(9)S_(8)@CC electrode requires a low cell voltage of 1.53 V at 10 mA cm^(-2)and shows excellent stability and splendid reversibility,demonstrating a huge potential for affordable and scalable electrochemical H_(2) production.The innovational orbital hybridization strategy for electronic regulation herein provides an inspirable avenue for developing progressive electrocatalysts toward new energy systems.展开更多
Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has gar...Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has garnered significant interest due to its remarkable properties such as negative/zero thermal expansion and magnetocaloric effects.However,when utilized as hydrogen evolution catalysts,it encounters large challenge resulting from excessively strong/weak interactions with adsorbed H on Mn/Cu active sites,which leads to low HER activity.In this study,we introduce an asymmetric orbital hybridization strategy in Zn-doped Cu_(1-x)Zn_(x)NMn_(3)by leveraging the localization of Zn electronic states to reconfigure the electronic structures of Cu and Mn,thereby reducing the energy barrier for water dissociation and optimizing Cu and Mn active sites for hydrogen adsorption and H_(2)production.Electrochemical evaluations reveal that Cu_(0.85)Zn_(0.15)NMn_(3)with x=0.15 demonstrates exceptional electrocatalytic activity in alkaline electrolytes.A low overpotential of 52 mV at 10 mA cm^(-2)and outstanding stability over a 150-h test period are achieved,surpassing commercial Pt/C.This research offers a novel strategy for enhancing HER performance by modulating asymmetric hybridization of electron orbitals between multiple metal atoms within a material structure.展开更多
In overlapping distribution areas of Sorbus pohuashanensis and S.discolor in North China(Mount Tuoliang,Mount Xiling and Mount Baihua),Sorbus indi-viduals were found with pink fruit,which have never been recorded for ...In overlapping distribution areas of Sorbus pohuashanensis and S.discolor in North China(Mount Tuoliang,Mount Xiling and Mount Baihua),Sorbus indi-viduals were found with pink fruit,which have never been recorded for the flora of China.Fourteen morphological characters combined with four chloroplast DNA markers and internal transcribed spacer(ITS)were used to analyze the origin of the Sorbus individuals with pink fruits and their relationship to S.pohuashanensis and S.discolor.PCA,SDA and one-way(taxon)ANOVA of morphological characters provided convincing evidence of the hybrid ori-gin of Sorbus individuals with pink fruits based on a novel morphological character and many intermediate characters.Haplotype analysis based on four cpDNA markers showed that either S.pohuashanensis or S.discolor were maternal parents of Sorbus individuals with pink fruits.Incongru-ence of the position of Sorbus individuals with pink fruits between cpDNA and ITS in cluster trees supported by DNA sequence comparative analysis,implying former hybridiza-tion events between S.pohuashanensis and S.discolor.Mul-tiple hybridization events between S.pohuashanensis and S.discolor might have contributed to the generation of Sorbus individuals with pink fruits.This study has provided insights into hybridization between species of the same genus in sympatric areas,which is of great significance for the study of interspecific hybridization.展开更多
Supercapacitors are gaining popularity due to their high cycling stability,power density,and fast charge and discharge rates.Researchers are ex-ploring electrode materials,electrolytes,and separat-ors for cost-effecti...Supercapacitors are gaining popularity due to their high cycling stability,power density,and fast charge and discharge rates.Researchers are ex-ploring electrode materials,electrolytes,and separat-ors for cost-effective energy storage systems.Ad-vances in materials science have led to the develop-ment of hybrid nanomaterials,such as combining fil-amentous carbon forms with inorganic nanoparticles,to create new charge and energy transfer processes.Notable materials for electrochemical energy-stor-age applications include MXenes,2D transition met-al carbides,and nitrides,carbon black,carbon aerogels,activated carbon,carbon nanotubes,conducting polymers,carbon fibers,and nanofibers,and graphene,because of their thermal,electrical,and mechanical properties.Carbon materials mixed with conducting polymers,ceramics,metal oxides,transition metal oxides,metal hydroxides,transition metal sulfides,trans-ition metal dichalcogenide,metal sulfides,carbides,nitrides,and biomass materials have received widespread attention due to their remarkable performance,eco-friendliness,cost-effectiveness,and renewability.This article explores the development of carbon-based hybrid materials for future supercapacitors,including electric double-layer capacitors,pseudocapacitors,and hy-brid supercapacitors.It investigates the difficulties that influence structural design,manufacturing(electrospinning,hydro-thermal/solvothermal,template-assisted synthesis,electrodeposition,electrospray,3D printing)techniques and the latest car-bon-based hybrid materials research offer practical solutions for producing high-performance,next-generation supercapacitors.展开更多
基金supported by the National Key R&D Program of China(Grant No.2022YFA1402902)the National Natural Science Foundation of China(Grant Nos.12374179,12074119,12374145,051B22001,12104157,12134003,and 12304218)the Shanghai Pujiang Program(Grant No.23PJ1402200).
文摘The hybridization between oxygen 2p and transition-metal 3d states largely determines the electronic structure near the Fermi level and related functionalities of transition-metal oxides(TMOs).Considerable efforts have been made to manipulate the p-d hybridization in TMOs by tailoring the spatial orbital overlap via structural engineering.Here,we demonstrate enhanced p-d hybridization in Ba^(2+)-doped LaNiO_(3)epitaxial films by simultaneously modifying both the spatial and energetic overlaps between the O-2p and Ni-3d orbitals.Combining x-ray absorption spectroscopy and firstprinciples calculations,we reveal that the enhanced hybridization stems from the synergistic effects of a reduced chargetransfer energy due to hole injection and an increased spatial orbital overlap due to straightening of Ni-O-Ni bonds.We further show that the enhanced p-d hybridization can be utilized to promote the oxygen evolution activity of LaNiO_(3).This work sheds new insights into the fine-tuning of the electronic structures of TMOs for enhanced functionalities.
基金supported by the National Natural Science Foundation of China(32171816)T4F program Sweden.
文摘Hybridization is a driving force in ecological transitions and speciation,yet direct evidence linking it to adaptive differentiation in natural systems remains limited.This study evaluates the role of hybridization in the speciation of Pinus densata,a keystone forest species on the southeastern Tibetan Plateau.By creating artificialinterspecificF1s and a long-term common garden experiment on the plateau,we provide in situ assessments on 44 growth and physiological traits across four seasons,along with RNA sequencing.We found significantphenotypic divergence between P.densata and its putative parental species P.tabuliformis and P.yunnanensis,with P.densata demonstrating superior growth and dynamic balance between photosynthesis and photoprotection.The F1s closely resembled P.densata in most traits.Gene expression revealed 19%–10%of 34,000 examined genes as differentially expressed in P.densata and F1s relative to mid-parent expression values.Both additive(4%)and non-additive gene actions(5%–6%in F1s,10%–12%in P.densata)were common,while transgressive expression occurred more frequently in the stabilized natural hybrids,illustrating transcriptomic reprogramming brought by hybridization and further divergence by natural selection.We provide compelling evidence for hybridization-derived phenotypic divergence at both physiological and gene expression levels that could have contributed to the adaptation of P.densata to high plateau habitat where both parental species have low fitness.The altered physiology and gene expression in hybrids serve both as a substrate for novel ecological adaptation and as a mechanism for the initiation of reproductive isolation.
基金financial support of the National Natural Science Foundation of China (22379063)
文摘Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.Herein,we find that oxygen vacancies can significantly boost the capacity,electrochemical kinetics,and structure stability of LDHs.The corresponding structure-performance relationship and energy storage mechanism are elaborated through exhaustive in/ex-situ experimental characterizations and density functional theory(DFT)calculations.Specially,in-situ Raman and DFT calculations reveal that oxygen vacancies elevate orbital energy of O 2p and electron density of O atoms,thereby enhancing the orbital hybridization of O 2p with Ni/Co 3d.This facilitates electron transfer between O and adjacent Ni/Co atoms and improves the covalency of Ni–O and Co–O bonds,which activates Ni/Co atoms to release more capacity and stabilizes the Ov-NiCo-LDH structure.Moreover,the distribution of relaxation times(DRT)and molecular dynamics(MD)simulations disclose that the enhanced d-p orbital hybridization optimizes the electronic structure of Ov-NiCo-LDH,which distinctly reduces the diffusion energy barriers of Mg^(2+)and improves the charge transfer kinetics of Ov-NiCo-LDH.Consequently,the assembled Ov-NiCo-LDH//active carbon(AC)and Ov-NiCo-LDH//perylenediimide(PTCDI)AMIBs can both deliver high specific discharge capacity(182.7 and 59.4 mAh g^(−1)at 0.5 A g^(−1),respectively)and long-term cycling stability(85.4%and 89.0%of capacity retentions after 2500 and 2400 cycles at 1.0 A g^(−1),respectively).In addition,the practical prospects for Ov-NiCo-LDH-based AMIBs have been demonstrated in different application scenarios.This work not only provides an effective strategy for obtaining high-performance cathodes of AMIBs,but also fundamentally elucidates the inherent mechanisms.
文摘Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains unclear.Additionally,the modulation of reactive oxygen species in Fenton-like reactions remains challenging.Herein,a novel strategy is reported for the rational design of highly loaded Co ASACs(CoN_(1)C_(2)/C_(2)N)immobilized on three-dimensional flower-like C_(2)N using an in situ-generated carbon defect method.In particular,the asymmetrically tricoordinated CoN_(1)C_(2)/C_(2)N exhibited excellent catalytic activity for sulfachloropyridazine degradation,with a turnover frequency of 36.8 min^(–1).Experimental results and theoretical calculations revealed that the electron spin state of the Co-active sites was transferred from the low-spin configuration(t_(2g)^(6)e_(g)^(1))to the high-spin configuration(t_(2g)^(5)e_(g)^(2))owing to asymmetric coordination.The high-spin Co 3d orbital in CoN_(1)C_(2)/C_(2)N possessed more unpaired electrons and therefore,had a strong ability to gain electrons from the O 2p orbitals of HSO_(5)^(–),boosting d-p orbital hybridization.More importantly,the spin-electron filling in theσ^(*)orbital of high-spin Co 3d−O 2p accelerated the desorption of^(*)SO_(5)•^(−),which acted as a rate-limiting step in the reaction,thus facilitating more^(1)O_(2)generation.This study provides an innovative synthetic route for practical ASACs and clarifies the critical relationship between structure and spin state,paving the way for advancements in environmental remediation and energy conversion applications.
基金supported by the National Natural Science Foundation of China(No.32161143024,31970405)Iran National Science Foundation,Iran-China(INSF-NSFC)joint project(No.4002006).
文摘The biological species concept defines species as groups of actually or potentially interbreeding natural populations that are reproductively isolated from other such groups(Mayr,1942).Reproductive isolation,whether prezygotic or postzygotic,plays a central role in maintaining species boundaries.However,hybridization between closely related taxa can challenge these boundaries and provide insight into speciation,gene flow,and evolutionary processes(Coyne and Orr,2004).
基金supported by Guangzhou Development Zone Science and Technology(2021GH10,2020GH10,2023GH02)the University of Macao(MYRG2022-00271-FST)The Science and Technology Development Fund(FDCT)of Macao(0032/2022/A).
文摘Introduction Early cancer detection represents a critical evolution in healthcare,addressing a significant pain point in cancer treatment:the tendency for diagnoses to occur at advanced stages.Traditionally,many cancers are not identified until they have progressed to late stages,where treatment options become limited,less effective,and more costly.This late detection results in poorer prognoses,higher mortality rates,and increased healthcare costs.Without early detection tools like Fluorescence In Situ Hybridization(FISH),these challenges persist,leaving patients with fewer opportunities for successful outcomes.
文摘Photocatalytic hydrogen(H_(2))production using solar energy is a cutting-edge green technology that holds great potential for addressing the urgent fuel and environmental crises[1–3].To achieve high-efficiency H_(2) production,cocatalyst modification is commonly employed to provide active sites for the hydrogen evolution reaction(HER)[4,5].In this context,the kinetics of hydrogen adsorption and desorption at these active sites play a crucial role in enhancing overall photocatalytic H_(2) production efficiency.However,the H adsorption/desorption kinetics often exhibit a trade-off,presenting a significant challenge in achieving an optimal equilibrium between Hads and Hdes in many cocatalyst systems.Therefore,fine-tuning the active sites to optimize the H_(2) evolution kinetics is essential for improving photocatalytic activity[6].
基金supported in part by National Natural Science Foundation of China(Nos.22225505,22174097).
文摘DNA nanomaterials hold great promise in biomedical fields due to its excellent sequence programmability,molecular recognition ability and biocompatibility.Hybridization chain reaction(HCR)is a simple and efficient isothermal enzyme-free amplification strategy of DNA,generating nicked double helices with repeated units.Through the design of HCR hairpins,multiple nanomaterials with desired functions are assembled by DNA,exhibiting great potential in biomedical applications.Herein,the recent progress of HCR-based DNA nanomaterials for biosensing,bioimaging and therapeutics are summarized.Representative works are exemplified to demonstrate how HCR-based DNA nanomaterials are designed and constructed.The challenges and prospects of the development of HCR-based DNA nanomaterials are discussed.We envision that rationally designing HCR-based DNA nanomaterials will facilitate the development of biomedical applications.
基金supported by the National Natural Science Foundation of China(21905253,51973200,and 52122308)the Natural Science Foundation of Henan(202300410372)the National Supercomputing Center in Zhengzhou
文摘The rational design of metal single-atom catalysts(SACs)for electrochemical nitrogen reduction reaction(NRR)is challenging.Two-dimensional metal-organic frameworks(2DMOFs)is a unique class of promising SACs.Up to now,the roles of individual metals,coordination atoms,and their synergy effect on the electroanalytic performance remain unclear.Therefore,in this work,a series of 2DMOFs with different metals and coordinating atoms are systematically investigated as electrocatalysts for ammonia synthesis using density functional theory calculations.For a specific metal,a proper metal-intermediate atoms p-d orbital hybridization interaction strength is found to be a key indicator for their NRR catalytic activities.The hybridization interaction strength can be quantitatively described with the p-/d-band center energy difference(Δd-p),which is found to be a sufficient descriptor for both the p-d hybridization strength and the NRR performance.The maximum free energy change(ΔG_(max))andΔd-p have a volcanic relationship with OsC_(4)(Se)_(4)located at the apex of the volcanic curve,showing the best NRR performance.The asymmetrical coordination environment could regulate the band structure subtly in terms of band overlap and positions.This work may shed new light on the application of orbital engineering in electrocatalytic NRR activity and especially promotes the rational design for SACs.
基金supported by the National Natural Science Foundation of China(Grant No.52090081)the State Key Laboratory of Hydro-science and Hydraulic Engineering(Grant No.2021-KY-04).
文摘Geological discontinuity(GD)plays a pivotal role in determining the catastrophic mechanical failure of jointed rock masses.Accurate and efficient acquisition of GD networks is essential for characterizing and understanding the progressive damage mechanisms of slopes based on monitoring image data.Inspired by recent advances in computer vision,deep learning(DL)models have been widely utilized for image-based fracture identification.The multi-scale characteristics,image resolution and annotation quality of images will cause a scale-space effect(SSE)that makes features indistinguishable from noise,directly affecting the accuracy.However,this effect has not received adequate attention.Herein,we try to address this gap by collecting slope images at various proportional scales and constructing multi-scale datasets using image processing techniques.Next,we quantify the intensity of feature signals using metrics such as peak signal-to-noise ratio(PSNR)and structural similarity(SSIM).Combining these metrics with the scale-space theory,we investigate the influence of the SSE on the differentiation of multi-scale features and the accuracy of recognition.It is found that augmenting the image's detail capacity does not always yield benefits for vision-based recognition models.In light of these observations,we propose a scale hybridization approach based on the diffusion mechanism of scale-space representation.The results show that scale hybridization strengthens the tolerance of multi-scale feature recognition under complex environmental noise interference and significantly enhances the recognition accuracy of GD.It also facilitates the objective understanding,description and analysis of the rock behavior and stability of slopes from the perspective of image data.
基金financially supported by the National Natural Science Foundation of China(21972068,22072067,22232004)the High-level Talents Project of Jinling Institute of Technology(jit-b-202164)。
文摘Precisely refining the electronic structure of electrocatalysts represents a powerful approach to further optimize the electrocatalytic performance.Herein,we demonstrate an ingenious d-d orbital hybridization concept to construct Mo-doped Co_(9)S_(8) nanorod arrays aligned on carbon cloth(CC)substrate(abbreviated as Mo-Co_(9)S_(8)@CC hereafter)as a high-efficiency bifunctional electrocatalyst toward water electrolysis.It has experimentally and theoretically validated that the 4d-3d orbital coupling between Mo dopant and Co site can effectively optimize the H_(2)O activation energy and lower H^(*)adsorption energy barrier,thereby leading to enhanced hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activities.Thanks to the unique electronic and geometrical advantages,the optimized Mo-Co_(9)S_(8)@CC with appropriate Mo content exhibits outstanding bifunctional performance in alkaline solution,with the overpotentials of 75 and 234 mV for the delivery of a current density of 10 mA cm^(-2),small Tafel slopes of 53.8 and 39.9 mV dec~(-1)and long-term stabilities for at least 32 and 30 h for HER and OER,respectively.More impressively,a water splitting electrolylzer assembled by the self-supported Mo-Co_(9)S_(8)@CC electrode requires a low cell voltage of 1.53 V at 10 mA cm^(-2)and shows excellent stability and splendid reversibility,demonstrating a huge potential for affordable and scalable electrochemical H_(2) production.The innovational orbital hybridization strategy for electronic regulation herein provides an inspirable avenue for developing progressive electrocatalysts toward new energy systems.
基金supported by the National Key R&D Program of China(No.2021YFB2800700)National Natural Science Foundation of China(Nos.12274210,62227820,and 12174183)+1 种基金Partial support is from NSF of Jiangsu Province(No.BK20220006)the Fundamental Research Funds for the Central Universities and Jiangsu Key Laboratory of Advanced Techniques for Manipulating Electromagnetic Waves。
文摘Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has garnered significant interest due to its remarkable properties such as negative/zero thermal expansion and magnetocaloric effects.However,when utilized as hydrogen evolution catalysts,it encounters large challenge resulting from excessively strong/weak interactions with adsorbed H on Mn/Cu active sites,which leads to low HER activity.In this study,we introduce an asymmetric orbital hybridization strategy in Zn-doped Cu_(1-x)Zn_(x)NMn_(3)by leveraging the localization of Zn electronic states to reconfigure the electronic structures of Cu and Mn,thereby reducing the energy barrier for water dissociation and optimizing Cu and Mn active sites for hydrogen adsorption and H_(2)production.Electrochemical evaluations reveal that Cu_(0.85)Zn_(0.15)NMn_(3)with x=0.15 demonstrates exceptional electrocatalytic activity in alkaline electrolytes.A low overpotential of 52 mV at 10 mA cm^(-2)and outstanding stability over a 150-h test period are achieved,surpassing commercial Pt/C.This research offers a novel strategy for enhancing HER performance by modulating asymmetric hybridization of electron orbitals between multiple metal atoms within a material structure.
基金This study was supported by the National Natural Science Foundation of China,Grant/Award Number:32071779.
文摘In overlapping distribution areas of Sorbus pohuashanensis and S.discolor in North China(Mount Tuoliang,Mount Xiling and Mount Baihua),Sorbus indi-viduals were found with pink fruit,which have never been recorded for the flora of China.Fourteen morphological characters combined with four chloroplast DNA markers and internal transcribed spacer(ITS)were used to analyze the origin of the Sorbus individuals with pink fruits and their relationship to S.pohuashanensis and S.discolor.PCA,SDA and one-way(taxon)ANOVA of morphological characters provided convincing evidence of the hybrid ori-gin of Sorbus individuals with pink fruits based on a novel morphological character and many intermediate characters.Haplotype analysis based on four cpDNA markers showed that either S.pohuashanensis or S.discolor were maternal parents of Sorbus individuals with pink fruits.Incongru-ence of the position of Sorbus individuals with pink fruits between cpDNA and ITS in cluster trees supported by DNA sequence comparative analysis,implying former hybridiza-tion events between S.pohuashanensis and S.discolor.Mul-tiple hybridization events between S.pohuashanensis and S.discolor might have contributed to the generation of Sorbus individuals with pink fruits.This study has provided insights into hybridization between species of the same genus in sympatric areas,which is of great significance for the study of interspecific hybridization.
文摘Supercapacitors are gaining popularity due to their high cycling stability,power density,and fast charge and discharge rates.Researchers are ex-ploring electrode materials,electrolytes,and separat-ors for cost-effective energy storage systems.Ad-vances in materials science have led to the develop-ment of hybrid nanomaterials,such as combining fil-amentous carbon forms with inorganic nanoparticles,to create new charge and energy transfer processes.Notable materials for electrochemical energy-stor-age applications include MXenes,2D transition met-al carbides,and nitrides,carbon black,carbon aerogels,activated carbon,carbon nanotubes,conducting polymers,carbon fibers,and nanofibers,and graphene,because of their thermal,electrical,and mechanical properties.Carbon materials mixed with conducting polymers,ceramics,metal oxides,transition metal oxides,metal hydroxides,transition metal sulfides,trans-ition metal dichalcogenide,metal sulfides,carbides,nitrides,and biomass materials have received widespread attention due to their remarkable performance,eco-friendliness,cost-effectiveness,and renewability.This article explores the development of carbon-based hybrid materials for future supercapacitors,including electric double-layer capacitors,pseudocapacitors,and hy-brid supercapacitors.It investigates the difficulties that influence structural design,manufacturing(electrospinning,hydro-thermal/solvothermal,template-assisted synthesis,electrodeposition,electrospray,3D printing)techniques and the latest car-bon-based hybrid materials research offer practical solutions for producing high-performance,next-generation supercapacitors.
